EP1183217B1 - Improved cement-based compositions - Google Patents

Improved cement-based compositions Download PDF

Info

Publication number
EP1183217B1
EP1183217B1 EP00915823A EP00915823A EP1183217B1 EP 1183217 B1 EP1183217 B1 EP 1183217B1 EP 00915823 A EP00915823 A EP 00915823A EP 00915823 A EP00915823 A EP 00915823A EP 1183217 B1 EP1183217 B1 EP 1183217B1
Authority
EP
European Patent Office
Prior art keywords
cement
metakaolin
based composition
composition according
dispersant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00915823A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1183217A1 (en
EP1183217A4 (en
Inventor
Karen Ann Gruber
John Hen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Catalysts LLC
Original Assignee
BASF Catalysts LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Catalysts LLC filed Critical BASF Catalysts LLC
Publication of EP1183217A1 publication Critical patent/EP1183217A1/en
Publication of EP1183217A4 publication Critical patent/EP1183217A4/en
Application granted granted Critical
Publication of EP1183217B1 publication Critical patent/EP1183217B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04Portland cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02Granular materials, e.g. microballoons
    • C04B14/04Silica-rich materials; Silicates
    • C04B14/10Clay
    • C04B14/106Kaolin
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/02Agglomerated materials, e.g. artificial aggregates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00Hydraulic cements
    • C04B7/12Natural pozzuolanas; Natural pozzuolana cements; Artificial pozzuolanas or artificial pozzuolana cements other than those obtained from waste or combustion residues, e.g. burned clay; Treating inorganic materials to improve their pozzuolanic characteristics

Definitions

  • This invention relates to novel metakaolin containing cement-based compositions.
  • metakaolin in cement
  • U.S. Patent 4,793,861 describes a cement-based product which is reinforced with glass fibers having good resistance to alkaline environments.
  • the product contains, for each 100 parts by weight of cement, about 10 to 40 parts by weight of metakaolin, the latter exhibiting a reactivity to the modified Chapelle test greater than 500 mg of CaO per gram of metakaolin.
  • U.S. Patent 4,842,649 describes a blended hydraulic cement composition composed of portland cement, slag, pozzolans including metakaolin, and admixtures including potassium carbonate and water reducing compositions.
  • U.S. Patent 4,975,396 describes a process for producing reinforced cementitious compositions in which the following constituents are mixed in the aqueous phase in the following order: about 35-55 parts by weight of water mixed with about 3-12 parts of a polymer, by weight of dry polymer; up to about 5 parts of a water-reducing auxiliary agent and/or a liquefying agent; from about 15-30 parts of metakaolin; from about 50-120 parts of silica sand; and about 100 parts of cement. Continuous mixing is maintained until a homogeneous, thixotropic paste is obtained. Then between 2 and 15% by weight of alkaline-resistant glass fibers, relative to the weight of the paste, is introduced into the paste.
  • U.S. Patent 4,994,114 describes method for selecting a pozzolan (for example metakaolin) for incorporation into a composite material comprising cement and glass.
  • a pozzolan for example metakaolin
  • GB 2294259 discloses a concrete admixture comprising metakaolin of ⁇ 2 micron and 2-50 wt.-% of an aqueous medium comprising a dispersing agent.
  • U.S. Patent 5,167,710 describes a process for making a cement mixture containing fibers wherein a paste is formed by mixing cement and, per 100 parts by weight of cement, approximately 5 to 20 parts by weight of a first pulverized material of which the grains have an average diameter of between 1/5 and 1/10 of the average diameter of the grains of the cement and approximately 20 to 35 parts by weight of water.
  • the paste is then mixed with reinforcing fibers.
  • the paste may also include a second pulverized material the average grain diameter of which is between 1/5 and 1/10 of the average diameter of the first pulverized material.
  • U.S. Patent 5,372,640 describes cement-based products reinforced with alkali-resistant glass fibers that become almost insensitive to aging when 30 to 40 parts by weight of a metakaolin composition are added for each 100 parts of cement.
  • U.S. Patent 5,624,489 describes a conversion-preventing additive for high-alumina cement-based compositions, the additive comprising: siliceous pozzolanic powder, e.g. zeolite, granulated blast-furnace slag, fly ash, silica fume, rice hulls, metakaolin; inorganic salts containing sodium or potassium cations and sulphate, carbonate, nitrate, silicate, phosphate, chloride or bromide anions, and optionally other chemical admixtures, e.g. superplasticizers.
  • siliceous pozzolanic powder e.g. zeolite, granulated blast-furnace slag, fly ash, silica fume, rice hulls, metakaolin
  • inorganic salts containing sodium or potassium cations and sulphate, carbonate, nitrate, silicate, phosphate, chloride or bromide anions e.g. superplasticizer
  • U.S. Patent 5,626,665 describes cementitious systems comprised of gypsum, calcined clay, and clinker.
  • Pozzolans are finely divided materials which can react with alkali to form cementitious products.
  • the fine particle size of pozzolans can lead to an increase in water demand.
  • the addition of extra water can reduce the performance of the system by reducing the strength and increasing the permeability of the resultant cement-based structures. The diminished strength is undesirable for several reasons. Initially, delay in early strength development results in surface cracking due to evaporation. Secondly, jobs take longer because the concrete form must remain in place substantially longer, and finishing is delayed.
  • the fine particle size of pozzolans can further lead to poor flowability of cement-based systems before setting. Therefore, there is still a need for improved pozzolans having lower water demand to produce a higher compressive strength while maintaining pozzolanic activity in cement-based systems. Since pozzolanic activity is associated with particle size, a material having finer particle size produces a more rapid pozzolanic reaction. As a result, most highly reactive pozzolans are, in produced form, fine powders with low bulk density. However, there is also still a need for pozzolans having improved flowability as a dry powder with a higher bulk density to reduce shipping and storage costs.
  • the present invention relates to a cement-based composition containing at least one cementitious material and at least one highly reactive metakaolin, wherein the highly reactive metakaolin is characterized as comprised of agglomerated beads of microparticles, the agglomerated beads having a median diameter of at least 10 microns and the microparticles having a median diameter of 5 micron or less.
  • the cement-based composition also comprises a dispersant.
  • the cement-based compositions of this invention are intended for use in cement-based applications such as swimming pool plasters, grouts, mortars and concrete.
  • the compositions of the present invention contain at least one cementitious material, at least one highly reactive pozzolan as specified in claim 1, and optionally at least one dispersant
  • the cement-based composition is the total combined dry mixture of the cementitious composition and highly reactive pozzolan materials which reacts with water to form the binder in concrete or other material.
  • Concrete is a construction material comprised of the cement-based composition, water, optional admixtures, and aggregates.
  • Cementitious materials include those materials typically required to make cement. Generally speaking, cementitious materials are binder materials that harden to form a connecting medium between solids. Cementitious materials include cements, which are any mixture of finely-ground lime, alumina, and silica that will set to a hard product that combines with other ingredients to form a hydrate such as portland cement, hydraulic cements, blended cement, and masonry cement, mortar, and related aggregate, admixtures and/or additives including hydrated lime, limestone, chalk, calcareous shell, talc, slag or clay.
  • cements which are any mixture of finely-ground lime, alumina, and silica that will set to a hard product that combines with other ingredients to form a hydrate such as portland cement, hydraulic cements, blended cement, and masonry cement, mortar, and related aggregate, admixtures and/or additives including hydrated lime, limestone, chalk, calcareous shell, talc, slag or clay.
  • Ordinary portland cement is a hydraulic cement produced by pulverizing portland cement clinker.
  • Portland cements are classified under ASTM standards ⁇ 150-95 into eight types, including: Type I for use in general concrete construction where the special properties specified for Types II, III, IV and V are not required; Type II for use in general concrete construction exposed to moderate sulphate action, or where moderate heat of hydration is required; Type III for use when high early strength is required; Type IV for use when low heat of hydration is required; Type V for use when high sulphate resistance is required; and Types IA, IIA and IIIA, which are the same as Types I, II, and III, respectively, except that they have an air entraining agent added.
  • "Ordinary portland cement" in the context of this invention includes all types (I-V and IA-IIIA) of portland cement as referenced in ASTM C 150-95.
  • the cement-based compositions of the present invention contain from about 50°/a to about 99.5% by weight of a cementitious material. In another embodiment, the cement-based compositions of the present invention contain from about 75% to about 99% by weight of a cementitious materials.
  • the cement-based compositions contain at least one highly reactive pozzolan, which is metakaolin.
  • the cement-based compositions according to the present invention have at least one of lower water demand, higher compressive strength, and higher flowability compared with cement-based compositions that do not contain a highly reactive pozzolan.
  • the cement-based compositions of the present invention contain from about 0.5% to about 50% by weight of the highly reactive pozzolan.
  • the cement-based compositions of the present invention contain from about 1% to about 25% by weight of the highly reactive metakaolin.
  • the cement-based compositions of the present invention contain from about 2% to about 20% by weight of the highly reactive metakaolin.
  • the highly reactive metakoalin is highly reactive in that composites having high compressive strengths are obtainable as a result of the present invention. That is, the components of the cement-based compositions of the present invention containing the highly reactive metakaolin react and set in such a manner that composites having high compressive strengths are obtained compared with cement-based compositions that do not contain the highly reactive metakaolin as described herein. Although the highly reactive metakaolin possesses little or no cementitious value, in the presence of moisture chemically reacts with calcium hydroxide at ordinary temperatures to form compounds possessing cementitious properties.
  • the highly reactive metakaolin is constituted by agglomerated beads of microparticles.
  • the agglomerated beads have a median particle size from 10 microns to 100 microns (above 10 microns), In another embodiment, the agglomerated beads have a median particle size from 15 microns to 50 microns (above 15 microns). In yet another embodiment, the agglomerated beads have an average particle size from 20 microns to 40 microns (above 20 microns).
  • the microparticles have a median particle size from 0.1 microns to 5 microns (5 microns or less). In another embodiment, the microparticles have a median particle size from 0.2 microns to 2 micron (2 micron or less). In yet another embodiment, the microparticles have a median particle size from 0.25 microns to 0.75 microns (0.75 microns or less).
  • the particle size distribution of the microparticles is about 95% of the microparticles are from 0.2 microns to 5 microns, In another preferred embodiment, the particle size distribution of the agglomerated beads is about 95% of the agglomerated beads are from 15 microns to 30 microns. In another embodiment, the agglomerated beads of the metakaolin particles have a median particle diameter of at least five times that of the constituent metakaolin microparticles. Microparticles smaller than about 0.1 microns do not typically negatively affect the performance of the agglomerated beads, but microparticles larger than about 10 microns should be minimized as they may reduce the physical integrity of the agglomerated beads of this invention.
  • particle size is determined by conventional sedimentation techniques using Micromeretics, Inc.'s SEDIGRAPH® 5100 particle size analyzer. Particles are slurried in water with a dispersant and pumped through the detector with agitation to disperse loose agglomerates.
  • the highly reactive metakaolin suitable for use in the present invention may be prepared by a process which comprises agglomerating a liquid slurry comprising at least one metakaolin.
  • the metakaolin combined with water has a particle size from 0.1 micron to 5 microns.
  • the desired particle size distributions of the metakaolin can be obtained by grinding or pulverizing larger particles of metakaolin and/or through screening, centrifuging, air classification, or other separating means for removing particles larger than about 10 microns.
  • Metakaolin is known to those of ordinary skill in the art and can be prepared by calcining hydrous kaolin, which is generally represented by the formula Al 2 O 3 •2SiO 2 •2H 2 O, where the water is present as interstitial water.
  • the metakaolin of this invention is typically made by calcination at temperatures from about 350°C to about 1000°C, more typically from about 500° to about 900°C.
  • the terms "metakaolin” and “metakaolinite” are used herein to mean an activated product of kaolinite, produced thermally or by any other means.
  • metakaolin is combined with a liquid to form a slurry.
  • the liquid is typically water but may also include organic liquids and water-organic liquid mixtures.
  • an effective amount of at least one dispersant is included in the slurry to facilitate the dispersion of the metakaolin. These dispersants may be preformed and added to the slurry or formed within the slurry.
  • the slurry is typically neutral, e.g., having a pH from about 6 to about 8, and preferably from about 6.5 to about 7.5.
  • the pH of the slurry may be adjusted, if necessary, by the addition of an acid or base so that the final pH of the slurry is approximately neutral.
  • Formation of the slurry is typically conducted at ambient temperature and at atmospheric pressure. Higher or lower temperatures and pressures may be used but are not necessary.
  • Dispersants suitable for use in the present invention include organic dispersants and inorganic dispersants.
  • Dispersants generally include ammonia-based dispersants and phosphate-based dispersants.
  • Dispersants further include sulfonate dispersants, carboxylic acid dispersants and polymeric dispersants, such as polyacrylate dispersants.
  • from about 0.1 % to about 20% by weight of the metakaolin of one or more dispersants is added to the slurry. In another embodiment, from about 0.5% to about 10% by weight of the metakaolin of one or more dispersants is added to the slurry. In yet another embodiment, from about 1 % to about 8% by weight of the metakaolin of one or more dispersants is added to the slurry.
  • Inorganic phosphate-based dispersants include diammonium phosphate, dipotassium phosphate, disodium phosphate, monoammonium phosphate, monopotassium phosphate, monosodium phosphate, potassium tripolyphosphate, sodium acid pyrophosphate, sodium hexametaphosphate, sodium tripolyphosphate, tetrapotassium pyrophosphate, tetrasodium pyrophosphate, tripotassium phosphate, trisodium phosphate, urea phosphate and mixtures thereof.
  • Sulfonate dispersants include naphthalene sulfonates, alkylnaphthalene sulfonates, ethoxylated alkylphenol sulfonates, petroleum sulfonates, fatty acid sulfonates, lignosulfonates, olefin sulfonates, amine sulfonates, and alkylaryl sulfonates.
  • Specific examples include those under the trade designation Morwet® available from Witco Corp., those under the trade designation Sellogen available from Henkel Corp., and those under the trade designation Emkapon available from Emkay Chemical Co.
  • Carboxylic acids include typically include organic acids and their corresponding salts containing from about 6 to about 25 carbon atoms. In another embodiment, carboxylic acids include typically include organic acids and their corresponding salts that contain from about 8 to about 20 carbon atoms.
  • Polyacrylates include polyacrylic acid, salts of acrylic copolymers, acrylic acid copolymers (for example with maleic acid), and ammonium or alkali metal polyacrylates and polycarboxylate salts. Specific examples include those under the trade designations Acumer® and Acusol available from Rohm & Haas Co., those under the trade designation Colloid available from Rhone-Poulenc Corp., and those under the trade designation Mayosperse available from Mayo Chemical.
  • the cement-based compositions and/or the pozzolan composition also contain at least one of water reducers and superplasticizers.
  • a minor amount of a flocculating agent may also be incorporated into the mixture to facilitate dispersion/suspension of the particles in the liquid medium.
  • materials other than metakaolin may be incorporated into the mixture.
  • a minor amount of special water-soluble or water-dispersible sorbents e.g., silicas, aluminas or other clays
  • silicas, aluminas or other clays to selectively adsorb sulfur, soaps, phosphorous or other deleterious compounds may be incorporated into the mixture and end up in the agglomerated beads.
  • Additional additive materials include gypsum, alkali salts, hydrated kiln dust, hydrated lime, fly ash, plasticizing agents, etc.
  • the cement-based compositions and/or the highly reactive pozzolans contain a binder such as carboxymethyl cellulose, polyvinyl alcohol and/or polyvinylpyrrolidone.
  • the cement-based compositions and/or the highly reactive pozzolans do not contain a binder such as carboxymethyl cellulose, polyvinyl alcohol and/or polyvinylpyrrolidone.
  • the highly reactive pozzolan composition does not contain a binder such as carboxymethyl cellulose, polyvinyl alcohol and/or polyvinylpyrrolidone.
  • the cement-based compositions and/or the highly reactive pozzolans contain a minor amount of at least one binder material, preferably a water dispersible binder.
  • a "water dispersible binder” shall mean that under typical process conditions, the binder is soluble in water or other liquid medium or is sufficiently dispersed or suspended therein.
  • Binders suitable for use within the context of the present invention include alginates, dextrin, glucose, gums, starch, waxes, glues; polymeric compounds such as poly(vinylacetate); mineral acids such as sulfuric acid and phosphoric acid; phosphates such as ammonium phosphate; silica compounds such as alkaline silicates and silica hydrosol; and colloidal clays such as attapulgite.
  • These binder materials are typically present in an amount up to about 10% by weight of the highly reactive pozzolan on a moisture-free basis, preferably from about 1% to about 5% by weight.
  • the polymer compound, if present as the only binder is present in an amount up to about 3% by weight of the highly reactive pozzolan on a moisture-free basis; and the colloidal clay, if present as the only binder, is present in an amount up to about 5% by weight of the highly reactive pozzolan on a moisture-free basis (as used herein in this context means the weight achieved after heating to a constant weight at about 250°F).
  • the agglomeration of the metakaolin; that is the formation of the agglomerated beads can be carried out by spray drying the slurry, flash drying the slurry, rotary drying, mixing the slurry or other conglomeration techniques. Flash drying techniques are known in the clay industry. Spray drying techniques are known in the clay industry. As a reference, consult e.g., " Atomization and Spray Drying," by W. R. Marshall (Chemical Engineering Monograph Series, No. 2, Vol. 50 (1954 )).
  • the mixture of metakaolin, liquid (preferably water) and optional additives or ingredients is adjusted, if necessary, by the addition of liquid so that the metakaolin slurry is pumpable and sprayable,
  • the concentration of metakaolin in the slurry is at least 40% by weight of the slurry.
  • the concentration of metakaolin in the slurry is at least 50% by weight of the slurry.
  • the concentration of metakaolin in the slurry is at least 60% by weight of the slurry. It is noted that due to rheological considerations, smaller interactive particles tend to make a viscous mix, so transport properties depend on the size of the particles as well as their concentration.
  • the mixture or slurry is then sprayed into an atmosphere of hot, inert (to this product) gases.
  • Spray dryers of various designs can be used. These dryers may be of the concurrent, countercurrent, or mixed flow type. Nozzles, disks or the like can be used to disperse the slurry into droplets.
  • the temperature of the inlet and outlet air of the spray dryer will depend, of course, on the design of the dryer.
  • the actual internal temperature of the agglomerated beads in the drying chamber should be below 107°C (225°F), for example from about 82°C to 93°C (180°F to 200°F). At these temperatures, there is very little or no change in the crystal structure of the clay (free water is eliminated but interstitial water is not eliminated).
  • the droplets thus become porous agglomerated beads of metakaolin and are collected downstream of the drying chamber, by the usual methods.
  • the air inlet temperature and the clay slurry feed rate are adjusted to produce an air outlet temperature within the range from about 121°C (250°F) to about 149°c (300°F).
  • the mixture of metakaolin, liquid (preferably water), and optional ingredients can be agglomerated in a mechanical mixer.
  • Mixing typically involves using a high-shear mixer.
  • a preferred type of mixer employs pins or blades mounted radially on a rotating shaft, so that the tip of the pin or blade, traveling at high speed, causes solid particles, binder and water to impinge upon or contact each other in such a way as to form an agglomerate.
  • nominally-spherical particles tend to grow larger and larger. This phenomenon is enhanced by the tips of the blades or pins coming very close to a stationary wall or to a solid object (e.g., another blade or pin) moving at a different relative rate.
  • the vortexes set up by this shearing motion tend to enhance the sphericity of the growing beads.
  • the present invention provides strong, porous agglomerated beads of metakaolin in the relatively small particle size range from about 10 to about 100 microns.
  • Size can be defined by any number of attrition tests. For example, agitating the product in oil and then measuring particle size or filter rate will give a relative measure of strength. Alternatively, if the product is transported pneumatically in a loop for a period of time, this can separate strong particles from weaker formulations.
  • the agglomerated beads contain from about 70% to about 100% by weight of metakaolin microparticles and from about 0% to about 30% of one or more dispersants and additives. In another embodiment, the agglomerated beads contain from about 80% to about 99% by weight of metakaolin microparticles and from about 1% to about 20% of one or more dispersants and additives. In yet another embodiment, the agglomerated beads contain from about 90% to about 98% by weight of metakaolin microparticles and from about 2% to about 10% of one or more dispersants and additives.
  • the agglomerated beads are combined with the cementitious material to form a cement-based composition.
  • Cement paste is made by adding water to the cement-based composition.
  • swimming pool plaster, grouts, concrete and mortar are made by combining water, the cement-based composition, and any desired aggregate, admixtures or additives.
  • ASTM C 109/109M-95 quantifies the flowability and the compressive strength of hydraulic cement mortars.
  • the compressive strength is the measured maximum resistance of a specimen to axial compressive loading normally expressed as force per unit cross-sectional area.
  • Two mortar compositions one composition according to the present invention and the other composition not according to the invention are made and compared.
  • a cement-based composition of 93% by weight mortar cement and 7% by weight of a spray-dried metakaolin in the form of agglomerated beads is combined with water with a water-to-cement ratio of 0.48.
  • a cement-based composition of 93% by weight mortar cement and 7% by weight of conventional metakaolin is combined with water with a water-to-cement ratio of 0.48.
  • the flowability is examined.
  • the results indicate the lower water demand of the composite made in accordance with the present invention.
  • 1.2% by weight of a superplasticizer chemical admixture is added to the first composition while 3.2% by weight of the same superplasticizer chemical admixture is added to the second composition (more superplasticizer chemical admixture is added to the second composition so that the second composition has the same flowability as the first composition).
  • the amount of water combined with the cement-based compositions according to the present invention is about 5% less than that required to obtain the same flowability compared to conventiontional cement-based compositions such as those made with conventional pozzolans including conventional metakaolin (other than water, the amounts of other components, such as optional additives, are the same). In another embodiment, the amount of water combined with the cement-based compositions according to the present invention is about 10% less than that required to obtain the same flowability compared to conventiontional cement-based compositions such as those made with conventional pozzolans including conventional metakaolin (other than water, the amounts of other components, such as optional additives, are the same).
  • the amount of water combined with the cement-based compositions according to the present invention is about 20% less than that required to obtain the same flowability compared to conventiontional cement-based compositions such as those made with conventional pozzolans including conventional metakaolin (other than water, the amounts of other components, such as optional additives, are the same). This is a notable improvement since a lower water demand is associated with an increase in density and an increase in strength.
  • Conventional cement-based compositions (those made with conventional pozzolans including conventional metakaolin) have a loose bulk density of 240kg/m 3 (15 lbs/ft 3 ) and a tamped bulk density of 449 kg/m 3 (28 lbs/ft 3 ).
  • the loose bulk density of cement-based compositions according to the present invention is at least about 400 kg/m 3 (25 lbs/ft 3 ) (according to ASTM D716-86).
  • the loose bulk density of cement-based compositions according to the present invention is at least about 481 kg/m 3 (30 lbs/ft 3 ) (according to ASTM D716-86).
  • the loose bulk density of cement-based compositions according to the present invention is at least about 529 kg/m 3 (33 lbs/ft 3 ) (according to ASTM D716-86).
  • the tamped bulk density of cement-based compositions according to the present invention is at least about 561 kg/m 3 (35 lbs/ft 3 ). In another embodiment, the tamped bulk density of cement-based compositions according to the present invention is at least about 641/m 3 (40 lbs/ft 3 ). In yet another embodiment, the tamped bulk density of cement-based compositions according to the present invention is at least about 721 kg/m 3 (45 lbs/ft 3 ).
  • the mortar compositions made in accordance with the present invention not only exhibited superior workability, but also superior compressive strength. It is difficult to simultaneously improve both workability and compressive strength, yet the present invention provides cement-based compositions exhibiting both improved workability and compressive strength.
  • the present invention also provides cement-based compositions having relatively high bulk densities (loose and/or tamped).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Dispersion Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
EP00915823A 1999-04-12 2000-02-22 Improved cement-based compositions Expired - Lifetime EP1183217B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US290057 1988-12-23
US09/290,057 US6027561A (en) 1999-04-12 1999-04-12 Cement-based compositions
PCT/US2000/004420 WO2000061515A1 (en) 1999-04-12 2000-02-22 Improved cement-based compositions

Publications (3)

Publication Number Publication Date
EP1183217A1 EP1183217A1 (en) 2002-03-06
EP1183217A4 EP1183217A4 (en) 2005-08-10
EP1183217B1 true EP1183217B1 (en) 2009-05-13

Family

ID=23114365

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00915823A Expired - Lifetime EP1183217B1 (en) 1999-04-12 2000-02-22 Improved cement-based compositions

Country Status (13)

Country Link
US (1) US6027561A (es)
EP (1) EP1183217B1 (es)
JP (1) JP4911821B2 (es)
AT (1) ATE431319T1 (es)
AU (1) AU772773B2 (es)
BR (1) BR0009722B1 (es)
CA (1) CA2369581C (es)
DE (1) DE60042204D1 (es)
DK (1) DK1183217T3 (es)
ES (1) ES2323747T3 (es)
MX (1) MXPA01010265A (es)
PT (1) PT1183217E (es)
WO (1) WO2000061515A1 (es)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008049294B4 (de) * 2007-09-26 2016-02-18 Ceramix Ag Bauprodukt in Form eines festen Baumaterial für die Herstellung und/oder Verkleidung einer Gebäudehülle

Families Citing this family (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6221148B1 (en) * 1999-11-30 2001-04-24 Engelhard Corporation Manufacture of improved metakaolin by grinding and use in cement-based composites and alkali-activated systems
US6416574B1 (en) 2000-07-12 2002-07-09 Southern Ionica Incorporated Method and apparatus for recycling cement kiln dust
US20020081247A1 (en) * 2000-12-26 2002-06-27 Dodson Christopher E. Apparatus and method for producing amorphous silica ash
US6648962B2 (en) 2001-09-06 2003-11-18 W. R. Grace & Co.-Conn. Micro-granulose particulates
US20040106704A1 (en) * 2001-09-18 2004-06-03 Christian Meyer Admixture to improve rheological property of composition comprising a mixture of hydraulic cement and alumino-silicate mineral admixture
FI115046B (fi) * 2001-11-01 2005-02-28 Kautar Oy Hydraulisesti kovettuva sideaineseos ja menetelmä sen valmistamiseksi
NL1020205C2 (nl) 2002-03-19 2003-09-23 Cdem Holland Bv Werkwijze voor het opwerken van materiaal dat een pozzolane component bevat.
US6863837B2 (en) * 2002-08-05 2005-03-08 Geo Specialty Chemicals, Inc. Dispersant composition
US20040149174A1 (en) * 2003-02-05 2004-08-05 Mbt Holding Ag Accelerating admixture for concrete
US20040211342A1 (en) * 2003-04-25 2004-10-28 Mbt Holding Ag Rheology stabilizer for cementitious compositions
ES2224877B1 (es) * 2003-08-22 2006-03-01 Asociacion De Investigacion De Industrias De La Construccion Aidico. Procedimiento de diseño morfologico de puzolanas para el control de las caracteristicas tecnicas de los cementos a los que se adicionan.
US7700017B2 (en) * 2003-08-25 2010-04-20 Icestone Llc Method for producing materials from recycled glass and cement compositions
US7442248B2 (en) * 2003-11-18 2008-10-28 Research Incubator, Ltd. Cementitious composition
US20060166834A1 (en) * 2004-02-10 2006-07-27 Halliburton Energy Services, Inc. Subterranean treatment fluids comprising substantially hydrated cement particulates
US8183186B2 (en) 2004-02-10 2012-05-22 Halliburton Energy Services, Inc. Cement-based particulates and methods of use
US9512346B2 (en) * 2004-02-10 2016-12-06 Halliburton Energy Services, Inc. Cement compositions and methods utilizing nano-hydraulic cement
US7341104B2 (en) * 2004-02-10 2008-03-11 Halliburton Energy Services, Inc. Methods of using substantially hydrated cement particulates in subterranean applications
US7086466B2 (en) * 2004-02-10 2006-08-08 Halliburton Energy Services, Inc. Use of substantially hydrated cement particulates in drilling and subterranean applications
DE102004012536A1 (de) * 2004-03-15 2005-10-06 Stephan Schmidt Kg Zusatzstoff für die Herstellung erdfeuchter Betonerzeugnisse sowie Verfahren zum Herstellen derartiger Betonerzeugnisse
DE102005018650B4 (de) 2005-04-21 2009-07-23 Bene_Fit Gmbh Verwendung von kalziniertem Kaolin für Oberflächenbeschichtungen
WO2007016347A1 (en) * 2005-07-29 2007-02-08 Specialty Composites, Llc Cement-containing composition for use with alkali-resistant fiberglass and poles made therefrom
US20070079733A1 (en) * 2005-10-10 2007-04-12 David Crocker Cementitious mix with fibers
FI122360B (fi) * 2005-11-18 2011-12-30 Nordkalk Oy Ab Hydrauliseen sideaineeseen perustuva vesisuspensio ja menetelmä sen valmistamiseksi
FI122343B (fi) * 2005-11-18 2011-12-15 Nordkalk Oy Ab Menetelmä ja laitteisto kiintoainesuspensioiden valmistamiseksi
FR2898353B1 (fr) * 2006-03-07 2008-05-02 Lafarge Aluminates Sa Liant pour beton refractaire, preparation pour beton refractaire, beton refractaire et procede de fabrication
US8070895B2 (en) 2007-02-12 2011-12-06 United States Gypsum Company Water resistant cementitious article and method for preparing same
ES2304875B1 (es) * 2007-03-16 2009-11-11 Asoc. De Investigacion De Industrias De La Construccion Aidico-Instituto Tecnologico De Construccion Cemento portland adicionado con puzolanas texturizadas.
US9199879B2 (en) 2007-05-10 2015-12-01 Halliburton Energy Serives, Inc. Well treatment compositions and methods utilizing nano-particles
US9512351B2 (en) 2007-05-10 2016-12-06 Halliburton Energy Services, Inc. Well treatment fluids and methods utilizing nano-particles
US8586512B2 (en) 2007-05-10 2013-11-19 Halliburton Energy Services, Inc. Cement compositions and methods utilizing nano-clay
US9206344B2 (en) 2007-05-10 2015-12-08 Halliburton Energy Services, Inc. Sealant compositions and methods utilizing nano-particles
US8476203B2 (en) * 2007-05-10 2013-07-02 Halliburton Energy Services, Inc. Cement compositions comprising sub-micron alumina and associated methods
US8685903B2 (en) 2007-05-10 2014-04-01 Halliburton Energy Services, Inc. Lost circulation compositions and associated methods
US20090029141A1 (en) * 2007-07-23 2009-01-29 United States Gypsum Company Mat-faced gypsum board and method of making thereof
FI20085227L (fi) * 2008-03-14 2009-09-15 Kautar Oy Lujitettu huokoinen kuitutuote
FI123552B (fi) 2008-10-01 2013-07-15 Kautar Oy Strukturoitu sideainekoostumus
US7799128B2 (en) * 2008-10-10 2010-09-21 Roman Cement, Llc High early strength pozzolan cement blends
US8329308B2 (en) * 2009-03-31 2012-12-11 United States Gypsum Company Cementitious article and method for preparing the same
EP2253600A1 (en) * 2009-05-14 2010-11-24 Aalborg Portland A/S Portland limestone calcined clay cement
CN102648166A (zh) * 2009-10-16 2012-08-22 湖首大学 用于水硬性水泥的基于多元醇的掺合剂
US8414700B2 (en) 2010-07-16 2013-04-09 Roman Cement, Llc Narrow PSD hydraulic cement, cement-SCM blends, and methods for making same
WO2013059339A1 (en) 2011-10-20 2013-04-25 Roman Cement, Llc Particle packed cement-scm blends
US9272953B2 (en) 2010-11-30 2016-03-01 Roman Cement, Llc High early strength cement-SCM blends
US9169159B2 (en) 2013-03-15 2015-10-27 Jerry Setliff Cementitious composition
US10131575B2 (en) 2017-01-10 2018-11-20 Roman Cement, Llc Use of quarry fines and/or limestone powder to reduce clinker content of cementitious compositions
US10737980B2 (en) 2017-01-10 2020-08-11 Roman Cement, Llc Use of mineral fines to reduce clinker content of cementitious compositions
US11168029B2 (en) 2017-01-10 2021-11-09 Roman Cement, Llc Use of mineral fines to reduce clinker content of cementitious compositions
US10730805B2 (en) 2017-01-10 2020-08-04 Roman Cement, Llc Use of quarry fines and/or limestone powder to reduce clinker content of cementitious compositions

Family Cites Families (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3374056A (en) * 1964-12-03 1968-03-19 Grace W R & Co Process for increasing the thermal stability of synthetic faujasite
US3293192A (en) * 1965-08-23 1966-12-20 Grace W R & Co Zeolite z-14us and method of preparation thereof
JPS5350229A (en) * 1976-10-19 1978-05-08 Kondo Renichi Compound of cement
US4642137A (en) * 1985-03-06 1987-02-10 Lone Star Industries, Inc. Mineral binder and compositions employing the same
US4640715A (en) * 1985-03-06 1987-02-03 Lone Star Industries, Inc. Mineral binder and compositions employing the same
DE3619363A1 (de) * 1986-06-09 1987-12-10 Brockhues Chem Werke Ag Verfahren zum einfaerben von beton
FR2601356B1 (fr) * 1986-07-10 1992-06-05 Saint Gobain Vetrotex Produit a base de ciment arme de fibres de verre.
US4842649A (en) * 1987-10-02 1989-06-27 Pyrament, Inc. Cement composition curable at low temperatures
AU613982B2 (en) * 1987-11-27 1991-08-15 Ecc International Limited Porous inorganic material
FR2634193B1 (fr) * 1988-07-13 1993-03-26 Sogea Produit a base de ciment contenant du metakaolin
US5074475A (en) * 1990-03-26 1991-12-24 E.C.C. America Inc. Method for improving bulk density and flowability of calcined kaolin clay products
FR2661903B1 (fr) * 1990-05-11 1992-08-07 Rhone Poulenc Fibres Nouvelle composition cimentaire a base de ciment portland.
FR2665698B1 (fr) * 1990-08-10 1993-09-10 Conroy Michel Ciment complemente melange a des granulats selectionnes, pour l'obtention de mortier ou beton sans retrait, auto-lissant et auto-nivelant.
CH682561A5 (de) * 1990-09-03 1993-10-15 Holderbank Financ Glarus Tectoalumosilicat-Zement, daraus erhaltene Bindemittelmatrix, und Beton mit dieser Bindemittelmatrix.
JPH07187735A (ja) * 1993-11-12 1995-07-25 Sekisui Chem Co Ltd 硬化性無機質組成物
GB2294259A (en) * 1994-10-19 1996-04-24 Ecc Int Ltd Pozzolanic material for mortars and concrete
JPH08119696A (ja) * 1994-10-21 1996-05-14 Sekisui Chem Co Ltd 硬化性無機質組成物
JPH08165175A (ja) * 1994-12-08 1996-06-25 Sekisui Chem Co Ltd 発泡性無機質組成物
US5769936A (en) * 1995-01-09 1998-06-23 Mitsubishi Chemical Corporation Method for producing fly ash granules
US5624489A (en) * 1995-01-23 1997-04-29 National Research Council Of Canada Conversion-preventing additive for high alumina cement products
US5531824A (en) * 1995-05-25 1996-07-02 Burkes; J. Pate Method of increasing density and strength of highly siliceous cement-based materials
US5650004A (en) * 1995-06-20 1997-07-22 Yon; Michael D. Cement plaster composition, additive therefor and method of using the composition
AUPN504095A0 (en) * 1995-08-25 1995-09-21 James Hardie Research Pty Limited Cement formulation
JP2002515821A (ja) * 1995-12-08 2002-05-28 エンゲルハード・コーポレーシヨン 金属混入油原料分解用の触媒
DE19600445A1 (de) * 1996-01-09 1997-07-10 Wester Mineralien Gmbh Homogene ungehärtete Zusammensetzung auf Basis Zement
US5714002A (en) * 1997-02-12 1998-02-03 Mineral Resource Technologies, Llc Process for making a blended hydraulic cement
US5792251A (en) * 1997-02-14 1998-08-11 North American Refractories Co. Method of producing metakaolin
US6077495A (en) * 1997-03-03 2000-06-20 Engelhard Corporation Method, composition and system for the controlled release of chlorine dioxide gas
GB9712479D0 (en) * 1997-06-17 1997-08-20 Ecc Int Ltd Aqueous suspensions of inorganic particulate materials
EP0895972A1 (en) * 1997-08-08 1999-02-10 "HOLDERBANK" Financière Glarus AG Alkaline aluminoferrosilicate hydraulic cement
US5976240A (en) * 1997-09-08 1999-11-02 North American Refractories Co. Refractory system including reactive metakaolin additive

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008049294B4 (de) * 2007-09-26 2016-02-18 Ceramix Ag Bauprodukt in Form eines festen Baumaterial für die Herstellung und/oder Verkleidung einer Gebäudehülle

Also Published As

Publication number Publication date
BR0009722A (pt) 2002-01-02
DE60042204D1 (de) 2009-06-25
AU772773B2 (en) 2004-05-06
EP1183217A1 (en) 2002-03-06
CA2369581C (en) 2010-10-26
AU3703500A (en) 2000-11-14
US6027561A (en) 2000-02-22
JP4911821B2 (ja) 2012-04-04
ATE431319T1 (de) 2009-05-15
DK1183217T3 (da) 2009-08-10
CA2369581A1 (en) 2000-10-19
EP1183217A4 (en) 2005-08-10
WO2000061515A1 (en) 2000-10-19
BR0009722B1 (pt) 2009-01-13
JP2002541054A (ja) 2002-12-03
PT1183217E (pt) 2009-06-16
MXPA01010265A (es) 2002-03-07
ES2323747T3 (es) 2009-07-24

Similar Documents

Publication Publication Date Title
EP1183217B1 (en) Improved cement-based compositions
US6221148B1 (en) Manufacture of improved metakaolin by grinding and use in cement-based composites and alkali-activated systems
CA1334106C (en) Rice hull ash concrete admixture
US5693137A (en) Use of alumina clay with cement fly ash mixtures
JP2014501221A (ja) 軽量フライアッシュベースの骨材のインサイチュ製造のための方法
EP2145868A1 (en) Aqueous formulations
AU2011352932A1 (en) Method for in-situ manufacture of a lightweight fly ash based aggregate
CN100366564C (zh) 用于在水硬水泥中分散掺加料的颗粒添加剂
JPH0135789B2 (es)
El-Didamony et al. Hydration behavior of composite cement containing fly ash and nanosized-SiO2
US5122191A (en) Admixture and cement composition using same
JPH03265549A (ja) セメント混和材およびそれを用いたセメント組成物
SK280385B6 (sk) Zmes na žiaruvzdorné účely
Li On the Effects of PCE Superplasticizers in Low-carbon “Green” Cements Based on Calcined Clay and Slag
Li On the Effects of PCE Superplasticizers in Low-carbon Cements Based on Calcined Clay and Slag
SU1698218A1 (ru) Сырьева смесь дл изготовлени стеновых строительных изделий
CZ2006561A3 (cs) Zpusob výroby suchých maltových smesí
CS277371B6 (cs) Geopolymerní bezsádrovcový portlandský cement
JP2002255632A (ja) 人工骨材およびその製造方法
AU2002342434A1 (en) Particulate additive for dispersing admixtures in hydraulic cements

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20011012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

A4 Supplementary search report drawn up and despatched

Effective date: 20050628

RIC1 Information provided on ipc code assigned before grant

Ipc: 7C 04B 14/10 A

Ipc: 7C 04B 28/04 B

Ipc: 7C 04B 18/02 B

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF CATALYSTS LLC

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20090605

REF Corresponds to:

Ref document number: 60042204

Country of ref document: DE

Date of ref document: 20090625

Kind code of ref document: P

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: HEPP WENGER RYFFEL AG

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2323747

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20090401840

Country of ref document: GR

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20100216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090513

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100222

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 18

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20190225

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20190219

Year of fee payment: 20

Ref country code: ES

Payment date: 20190326

Year of fee payment: 20

Ref country code: GB

Payment date: 20190227

Year of fee payment: 20

Ref country code: IE

Payment date: 20190221

Year of fee payment: 20

Ref country code: CH

Payment date: 20190225

Year of fee payment: 20

Ref country code: IT

Payment date: 20190221

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20190225

Year of fee payment: 20

Ref country code: SE

Payment date: 20190222

Year of fee payment: 20

Ref country code: AT

Payment date: 20190227

Year of fee payment: 20

Ref country code: DK

Payment date: 20190225

Year of fee payment: 20

Ref country code: FR

Payment date: 20190227

Year of fee payment: 20

Ref country code: GR

Payment date: 20190227

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20190426

Year of fee payment: 20

Ref country code: PT

Payment date: 20190212

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 60042204

Country of ref document: DE

REG Reference to a national code

Ref country code: DK

Ref legal event code: EUP

Expiry date: 20200222

REG Reference to a national code

Ref country code: NL

Ref legal event code: MK

Effective date: 20200221

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20200221

REG Reference to a national code

Ref country code: FI

Ref legal event code: MAE

REG Reference to a national code

Ref country code: IE

Ref legal event code: MK9A

REG Reference to a national code

Ref country code: BE

Ref legal event code: MK

Effective date: 20200222

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK07

Ref document number: 431319

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200222

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20200221

Ref country code: IE

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20200222

Ref country code: PT

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20200305

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20200721

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20200223